JP6201513B2 - LAMINATE MANUFACTURING METHOD AND DEVICE STRUCTURE MANUFACTURING METHOD USING THE SAME - Google Patents

Description

  The present invention is a laminate of a polyimide film and a support such as an inorganic substrate, and a method for producing a laminate capable of easily separating the polyimide film from the support as required, and a device structure using the laminate It is related with the manufacturing method of a body.

  In recent years, for the purpose of reducing the weight, size and thickness of functional elements such as semiconductor elements, MEMS elements, and display elements, and increasing flexibility, technological developments for forming these elements on polymer films have been actively conducted. That is, as a material for the base material of electronic parts such as information communication equipment (broadcast equipment, mobile radio, portable communication equipment, etc.), radar, high-speed information processing equipment, etc. Ceramics that can cope with higher frequency bands (up to the GHz band) have been used, but since ceramics are not flexible and difficult to reduce in thickness, there is a drawback that applicable fields are limited. Is based on a polymer film.

  When functional elements such as semiconductor elements, MEMS elements, and display elements are formed on the surface of a polymer film, it is ideal to process them using a so-called roll-to-roll process that uses the flexibility of polymer films. It is said that. However, in the semiconductor industry, the MEMS industry, and the display industry, a process technology for a rigid flat substrate such as a wafer base or a glass substrate base has been constructed so far. Therefore, as a practical choice, a polymer film is bonded to a rigid support made of an inorganic material such as a glass plate, a ceramic plate, a silicon wafer, or a metal plate, and a desired element is formed thereon, and then supported. It is conceivable to peel from the body, which makes it possible to obtain a device structure composed of functional elements formed on a polymer film using existing infrastructure.

  Conventionally, bonding of a polymer film to a support made of an inorganic material has been widely performed using an adhesive or an adhesive. In the case where a desired functional element is formed on a laminate in which the polymer film thus obtained and a support made of an inorganic material are bonded together, a level of surface smoothness and dimensions that do not hinder the formation of the functional element. The laminated body is required to have stability, cleanliness, resistance to process temperature, resistance to chemicals used for fine processing, and the like. However, since conventional adhesives and pressure-sensitive adhesives for bonding did not have sufficient heat resistance, they cannot be applied when the functional element is formed at a high temperature.

  Therefore, a polymer film having a low melting point is not suitable from the viewpoint of heat resistance, and examples of the polymer film to be bonded to a support made of an inorganic material include polyethylene naphthalate, polyethylene terephthalate, polyimide, and polytetrafluoroethylene. A polymer film, glass fiber reinforced epoxy, or the like is used. In particular, a film made of polyimide has the advantage that it can be thinned because it has excellent heat resistance and is tough.

  As a production method using this polyimide film, Patent Document 1 describes a production method of a laminate comprising a support and a polyimide film. Specifically, as the polyimide film, a film having a plasma treatment applied to at least the surface facing the support is used, and a coupling agent is applied to at least one of the surfaces facing the support and the polyimide film. A coupling treatment layer is formed, and then a part of the coupling treatment layer is subjected to an inactivation treatment and subjected to a patterning treatment. It is carried out.

  However, in the said manufacturing method, after forming a coupling process layer and performing a patterning process with respect to a coupling process layer, a support body and a polyimide film are piled up. In this way, the coupling treatment layer surface is soiled by the process of patterning the coupling treatment layer from the coupling treatment layer formation to the superimposition of the support and the polyimide film, so that the surface of the coupling treatment layer is contaminated. There is a possibility that bubbles may be generated on the surface (device fabrication surface) where the polyimide film and the polyimide film overlap. If the surface of the coupling treatment layer becomes dirty, the peel strength between the support and the polyimide film may be reduced. And although the surface of a coupling process layer is easy to be contaminated or a foreign material tends to adsorb | suck, the contamination removal and foreign material removal of the surface are difficult. In addition, if bubbles are generated on the device fabrication surface, irregularities may occur on the device fabrication surface, and if a device is fabricated on the surface on which the irregularities have been produced, the pattern position of the device will be shifted, spots on the thin film will occur, and Problems such as variations in characteristics and broken lines in devices are likely to occur.

JP 2013-010342 A

  An object of the present invention is to provide a method for manufacturing a laminate that can reduce contamination on the surface of a coupling treatment layer and a method for manufacturing a device structure using the same.

  The present inventors completed the present invention by reducing the number of work steps for the coupling agent surface by performing a patterning process on the polyimide film and then adopting a manufacturing method in which the support and the polyimide film are superimposed. It came to do.

  This invention is a manufacturing method of the laminated body of a support body and a polyimide film, Comprising: The coupling process layer formation process of forming a coupling process layer with respect to the surface of the said support body facing the said polyimide film. A pattern forming step of forming a predetermined pattern by patterning a part of the surface of the polyimide film facing the support, a coupling treatment layer forming step, and a pattern forming step. And a pressure heat treatment step of superposing the support and the polyimide film on each other to perform a pressure heat treatment.

  The patterning process is an inactivation process, and the inactivation process is selected from the group consisting of a blast process, a vacuum plasma process, an atmospheric pressure plasma process, a corona process, an actinic radiation irradiation process, an active gas process, and a chemical solution process. It is preferable to perform at least one selected, and it is more preferable to perform at least UV irradiation treatment as the inactivation treatment.

  Before the pattern formation step, it is preferable to provide a plasma treatment step of performing a plasma treatment on the surface of the polyimide film facing the support.

  It is preferable to provide an acid treatment step for performing acid treatment on the polyimide film between the plasma treatment step and the pressure heat treatment step.

  The present invention also includes a method for producing a device structure, which is a method for producing a structure in which a device is formed on a polyimide film, and comprises a support, a polyimide film, and a coupling treatment layer. And forming a device on the polyimide film of the laminate, then cutting the polyimide film and peeling the polyimide film from the support. Features.

  The manufacturing method of the laminated body of the support body and polyimide film which concerns on this invention forms a coupling process layer on a support body, performs a patterning process with respect to a polyimide film, Then, a support body and a polyimide film are used. As a result, the work process on the surface of the coupling agent can be reduced, that is, the possibility that the surface of the coupling treatment layer is soiled can be reduced.

FIG. 1 is a schematic view showing an embodiment of a method for producing a laminate according to the present invention. FIG. 2 is a schematic view showing one embodiment of the method for producing a device structure of the present invention. FIG. 3 is a schematic view showing another embodiment of the device structure manufacturing method of the present invention. FIG. 4 is a schematic diagram showing a pattern example. FIG. 5 is an AFM image showing the crater portion. FIG. 6 is a cross-sectional AFM image of the straight portion of the crater portion shown in FIG. FIG. 7 is an AFM image (10 μm square) including a crater portion. FIG. 8 is an explanatory diagram for explaining a method of measuring the diameter of the crater portion. FIG. 9 is an explanatory diagram for explaining a method of measuring the number of craters.

  The manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body comprised from these using a support body and a polyimide film at least.

(Laminate manufacturing method)
The manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body of a support body and a polyimide film.

<Support>
The support in the present invention may be a plate made of an inorganic material that can be used as a substrate, for example, a glass plate, a ceramic plate, a silicon wafer, a metal wafer or the like mainly, and these glass plates, Examples of the ceramic plate, silicon wafer, and metal composite include those obtained by laminating them, those in which they are dispersed, and those containing these fibers.

  As the glass plate, quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), Borosilicate glass (microsheet), aluminosilicate glass and the like are included. Among these, those having a linear expansion coefficient of 5 ppm / ° C. or less are desirable, and if it is a commercial product, “Corning (registered trademark) 7059” or “Corning (registered trademark) 1737” manufactured by Corning, which is a glass for liquid crystal, “EAGLE”, “AN100” manufactured by Asahi Glass, “OA10” manufactured by Nippon Electric Glass, “AF32” manufactured by SCHOTT, etc. are desirable.

Examples of the ceramic plate include Al ₂ O ₃ , Mullite, AlN, SiC, Si ₃ N ₄ , BN, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO ₃ + Al ₂ O ₃ , Crystallized glass + Al ₂ O ₃ , Crystallized Catalysed. Ceramics for substrates such as BSG, BSG + Quartz, BSG + Al ₂ O ₃ , Pb + BSG + Al ₂ O ₃ , Glass-ceramic, Zerodur material, TiO ₂ , Strontium titanate, Calcium titanate, Magnesium titanate, MgO, Steatite, BaTi ₄ O ₉ , BaTiO ₃ , BaTi ₄ + CaZrO ₃ , BaSrCaZrTiO ₃ , Ba (TiZr) O ₃ , capacitor materials such as PMN-PT and PFN-PFW, PbN _{b 2 O 6, Pb 0.5 Be} 0.5 Nb 2 O 6, PbTiO 3, BaTiO 3, PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, a piezoelectric material such as PLZT is included.

  The silicon wafer includes all of n-type or p-type doped silicon wafers, intrinsic silicon wafers, etc., and silicon wafers in which a silicon oxide layer or various thin films are deposited on the surface of the silicon wafer. In addition to silicon wafers, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, and nitrogen-phosphorus-arsenic-antimony are often used. Furthermore, general-purpose semiconductor wafers such as InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), ZnSe (zinc selenide) are also included.

  Examples of the metal include single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as inconel, monel, mnemonic, carbon copper, Fe-Ni invar alloy, and super invar alloy. In addition, a multilayer metal plate formed by adding other metal layers and ceramic layers to these metals is also included. In this case, if the overall CTE (linear expansion coefficient) with the additional layer is low, Cu, Al or the like is also used for the main metal layer. The metal used as the additional metal layer is limited as long as it has properties such as strong adhesion to the polyimide film, no diffusion, good chemical resistance and heat resistance, etc. Although it is not, chromium, nickel, TiN, and Mo containing Cu are mentioned as a suitable example.

The planar portion of the support is desirably sufficiently flat. Specifically, the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If it is rougher than this, the peel strength between the polyimide film and the support may be insufficient.
<Polyimide film>
In general, a polyimide film is obtained by reacting a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent with a support for preparing a polyimide film (the support here is a laminate of the present invention). And a green film (also referred to as a “precursor film” or a “polyamic acid film”) by coating and drying on a support for making a polyimide film, Alternatively, it can be obtained by subjecting the green film to a high-temperature heat treatment in a state where it is peeled off from the support to cause a dehydration ring closure reaction.

  There is no restriction | limiting in particular as diamine which comprises a polyamic acid, The aromatic diamine, aliphatic diamine, alicyclic diamine etc. which are normally used for a polyimide synthesis | combination can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, it is possible to develop a high elastic modulus, a low heat shrinkage, and a low linear expansion coefficient as well as a high heat resistance. Diamines may be used alone or in combination of two or more.

  The molecular structure of aromatic diamines having a benzoxazole structure is not particularly limited, and specific examples include the following.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, “each isomer” means one in which the coordination positions of two amino groups of amino (aminophenyl) benzoxazole are different (for example, 5-amino-2- (p-aminophenyl) above) Benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole and 6-amino-2- (m-aminophenyl) benzoxazole And correspond to isomers).

  As the diamine, in addition to the diamine having the benzoxazole structure described above, other diamines exemplified below can be used. Examples of other diamines include 2,2′-bis (trifluoromethyl) benzidine, 2,2′-dimethyl-4,4′-diaminobiphenyl, bisaniline, and 1,4-bis (4-amino-2). -Trifluoromethylphenoxy) benzene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) ) Biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1, , 3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diaminodiphenyl ether, 3,4 ′ -Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3, 3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3, , 3 -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] Ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-amino) Phenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-Aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-a Minophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4 -Aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- (4-Aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,4-bis (3-aminophenyl) Noxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3- Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzo Ru] benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3- Aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-Aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3 -(3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino- α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α -Dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) ) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzen Benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy)- α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4′-diamino-4, 5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino- 5′-phenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 4,4′-diamino-5,5′-dibif Enoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4 '-Diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino -4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3- Amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benze 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino- [alpha], [alpha] -dimethylbenzyl) phenoxy] benzonitrile, 2,2'-bis (biphenyl) benzidine and some or all of the hydrogen atoms on the aromatic ring of the above aromatic diamine are halogen atoms, carbon atoms of 1 to 3 Aromatic diamines substituted with 1 to 3 halogenated alkyl groups or alkoxy groups in which some or all of the hydrogen atoms of the alkyl group or alkoxy group, cyano group, or alkyl group or alkoxy group are substituted with halogen atoms Etc. An alicyclic diamine such as 4,4'-methylenebis (2,6-dimethylcyclohexylamine) can also be used.

  When other diamines are used, the amount used is preferably 30 mol% or less of the total diamines, and more preferably 25 mol% or less.

  The tetracarboxylic acids constituting the polyamic acid are not particularly limited, and aromatic tetracarboxylic acids, aliphatic tetracarboxylic acids, alicyclic tetracarboxylic acids, or acid anhydrides thereof or the like usually used for polyimide synthesis are used. be able to. Among these, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, and aromatic tetracarboxylic acid anhydrides are more preferable. In the case where these are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydrides) are preferred. Good. Tetracarboxylic acids may be used alone or in combination of two or more.

  Examples of the alicyclic tetracarboxylic acid anhydride include cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetra. Examples thereof include carboxylic dianhydrides.

  Specific examples of aromatic tetracarboxylic acid anhydrides include the following.

The polyamic acid is particularly preferably composed of diamines and tetracarboxylic acids in the following combinations.
A. A combination of an aromatic tetracarboxylic acid having a pyromellitic acid residue and an aromatic diamine having a benzoxazole structure (skeleton).
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.

  In addition to the diamines and tetracarboxylic acids described above, the polyamic acid may contain tricarboxylic acids such as cyclohexane-1,2,4-tricarboxylic acid anhydride.

  The solvent used in the reaction (polymerization) of diamines and tetracarboxylic acids to obtain a polyamic acid is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. Solvents are preferred, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric Examples include amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents may be used alone or in combination of two or more. The amount of these solvents used may be an amount sufficient to dissolve the raw material monomer. As a specific amount used, the amount of all monomers in the reaction solution (solution in which the monomer is dissolved) is usually The amount is 5 to 40% by mass, preferably 7 to 30% by mass.

  The conditions for the polymerization reaction (hereinafter also simply referred to as “polymerization reaction”) for obtaining the polyamic acid may be conventionally known conditions, for example, in an organic solvent at a temperature range of 0 to 80 ° C. for 10 minutes. Stirring and / or mixing continuously for ˜30 hours. If necessary, the polymerization reaction may be divided or the reaction temperature may be increased or decreased. Although there is no restriction | limiting in particular in the addition order of a monomer, It is preferable to add tetracarboxylic acids in the solution of diamines.

  Further, vacuum degassing during the polymerization reaction is also effective for producing a good quality polyamic acid solution. Further, the polymerization may be controlled by adding a small amount of a terminal blocking agent to the diamine before the polymerization reaction. Examples of the terminal blocking agent include dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and aniline derivatives. Among these, specifically, phthalic anhydride, maleic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, and ethynylaniline are preferable, and maleic anhydride is particularly preferable. The amount of the end-capping agent used is preferably 0.001 to 1.0 mol with respect to 1 mol of the diamine.

  The mass of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The viscosity of the polyamic acid solution is preferably 10 to 2000 Pa · s, more preferably 100 to 1000 Pa · s, as measured by a Brookfield viscometer (25 ° C.), from the viewpoint of liquid feeding stability. .

  Various additives such as an antifoaming agent, a leveling agent, and a flame retardant may be added to the polyamic acid solution obtained by the polymerization reaction for the purpose of further improving the performance of the polyimide film. These addition methods and addition times are not particularly limited.

  In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (self-supporting precursor film) is obtained by applying and drying the polyamic acid solution on a polyimide film production support, Next, a method of imidizing the green film by subjecting it to a heat treatment can be employed. Application of polyamic acid solution to the support includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, casting from a nozzle with a slit, extruder However, the present invention is not limited thereto, and conventionally known solution coating means can be appropriately used. What is necessary is just to set the application quantity of a polyamic-acid solution suitably according to the film thickness of the desired polyimide film. The heating temperature for drying the applied polyamic acid solution is preferably 50 ° C to 120 ° C, more preferably 90 ° C to 110 ° C. The drying time is preferably 5 minutes to 3 hours, more preferably 15 minutes to 2 hours. The residual solvent amount in the green film after drying is preferably 25 to 50% by mass, and more preferably 35 to 45% by mass. The temperature at the time of heat-treating the green film is preferably, for example, 150 to 550 ° C, more preferably 280 to 520 ° C. The heat treatment time is desirably 0.05 to 10 hours.

  The polyimide film has a glass transition temperature of 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or preferably no glass transition point is observed in the region of 500 ° C. or lower. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC).

  The average coefficient of linear expansion (CTE) between 30 ° C. and 300 ° C. of the polyimide film is preferably −5 ppm / ° C. to +20 ppm / ° C., more preferably −5 ppm / ° C. to +15 ppm / ° C. Preferably, it is 1 ppm / ° C. to +10 ppm / ° C. When the CTE is in the above range, the difference in coefficient of linear expansion from a general support can be kept small, and the polyimide film and the support made of an inorganic material can be prevented from being peeled even when subjected to a process of applying heat. .

  Although the thickness of the polyimide film in this invention is not specifically limited, 1 micrometer-200 micrometers are preferable, More preferably, they are 3 micrometers-120 micrometers, More preferably, they are 3 micrometers-60 micrometers. It can be easily applied to narrow parts and can greatly contribute to the enhancement of the performance of elements such as sensors and the miniaturization of electronic parts. If the thickness of the polyimide film is less than 1 μm, it is difficult to strictly control the thickness, and peeling from the support becomes difficult. On the other hand, if it exceeds 200 μm, the polyimide film is bent when it is peeled off from the support. Is likely to occur.

The thickness unevenness of the polyimide film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow portions. In addition, the thickness unevenness of a film can be calculated | required based on the following formula, for example, extracting about 10 points | pieces positions from a film to be measured at random with a contact-type film thickness meter, measuring film thickness.
Film thickness spots (%)
= 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

  The polyimide film is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of production, and a form of a roll-shaped polyimide film wound on a winding core Are more preferred.

  In the polyimide film, in order to ensure handling and productivity, a sliding material (particle) is added to and contained in the polyimide constituting the film, and the surface of the polyimide film is given fine irregularities to ensure slipperiness. It is preferable.

  The above-mentioned lubricant (particles) are fine particles made of inorganic materials, such as metals, metal oxides, metal nitrides, metal carbonides, metal acid salts, phosphates, carbonates, talc, mica, clay, and other clay minerals. , Etc. can be used. Preferably, silica (silicon oxide), calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, and other metal oxides, phosphates, and carbonates can be used. . Only one type of lubricant may be used, or two or more types may be used.

  The volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 μm, preferably 0.03 to 2.5 μm, more preferably 0.05 to 0.7 μm, still more preferably 0.05 to 0.3 μm. The volume average particle diameter is based on a measurement value obtained by a light scattering method. If the particle diameter is smaller than the lower limit, it is difficult to industrially produce the polyimide film. If the particle diameter exceeds the upper limit, the surface irregularities become excessively large and the sticking strength becomes weak, which may cause practical problems.

  The addition amount of the lubricant is 0.05 to 50% by mass, preferably 0.07 to 6% by mass, and more preferably 0.1 to 0. 0% by mass with respect to the polymer solid content in the polyamic acid solution. 3% by mass. If the amount of the lubricant added is too small, it is difficult to expect the effect of the lubricant addition, and there is a case that the slipperiness is not secured so much that the polyimide film production may be hindered. Even if the sliding property is ensured, the smoothness may be lowered, the breaking strength and breaking elongation of the polyimide film may be lowered, and the CTE may be raised.

  When a lubricant (particle) is added to and contained in a polyimide film, it may be a single-layer polyimide film in which the lubricant is uniformly dispersed. For example, one surface is composed of a polyimide film containing a lubricant, Even if the other surface does not contain or contains a lubricant, a multilayer polyimide film composed of a polyimide film having a small amount of lubricant may be used. In such a multilayer polyimide film, fine irregularities are imparted to the surface of one layer (film), and slipperiness can be secured with the layer (film), and good handling properties and productivity can be secured. . Hereinafter, the production of such a multilayer polyimide film will be described.

  The multilayer polyimide film is, for example, a polyamic acid solution (polyimide precursor solution) with a lubricant (preferably having an average particle size of about 0.05 to 2.5 μm) of 0 per polymer solids in the polyamic acid solution. 0.05 to 50% by mass, preferably 0.07 to 6% by mass, more preferably 0.1 to 0.3% by mass and no lubricant or a small amount (preferably polyamide) It is preferable to produce using two polyamic acid solutions that are 0.3% by mass or less, more preferably 0.01% by mass or less) based on the solid content of the polymer in the acid solution.

  The method of multilayering (lamination) of the multilayer polyimide film is not particularly limited as long as no problem occurs in the adhesion between the two layers, and any method may be used as long as the adhesion is achieved without using an adhesive layer or the like. For example, i) a method in which one polyimide film is prepared and then the other polyamic acid solution is continuously applied onto the polyimide film to imidize; ii) one polyamic acid solution is cast to produce a polyamic acid film. After this, the other polyamic acid solution is continuously applied onto the polyamic acid film and then imidized, iii) a method by coextrusion, iv) a polyamic acid which does not contain a lubricant or has a small content Examples thereof include a method in which a polyamic acid solution containing a large amount of a lubricant is applied on a film formed by a solution by spray coating, T-die coating, or the like, and imidized. The methods i) and ii) are preferable.

  The ratio of the thickness of each layer in the multilayer polyimide film is not particularly limited, but the film (layer) formed of the polyamic acid solution containing a large amount of the lubricant (a) layer, does not contain the lubricant or contains it Assuming that the film (layer) formed of the polyamic acid solution in a small amount is the (b) layer, the (a) layer / (b) layer is preferably 0.05 to 0.95. If the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost. On the other hand, if it is less than 0.05, the effect of improving the surface properties is insufficient and the slipperiness is lost. May be.

  The polyimide film may be subjected to a plasma treatment process in which a plasma treatment is performed on a surface facing the support of the polyimide film (hereinafter referred to as an opposite surface of the polyimide film) before a patterning process described later. Preferably, the plasma treatment process is more preferably performed before the pattern forming process and the patterning process described below. By applying the plasma treatment, the surface of the polyimide film is modified to have a functional group (so-called activated state), and adhesion to the support is improved.

  The plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Also includes ion implantation using a source, processing using a PBII method, frame processing, intro processing, and the like. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF ₄ and C ₂ F _6, plasma known to have a high etching effect, or physical energy such as Ar plasma. It is desirable to use plasma with a high effect of applying to the polyimide surface and physically etching. Further, it is also preferable to add plasma such as CO ₂ , H ₂ , N ₂ , a mixed gas thereof, or water vapor. When aiming at processing in a short time, a plasma having a high plasma energy density, a high kinetic energy of ions in the plasma, and a high number density of active species are desirable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, PBII method, and the like are also desirable.

  The effects of plasma treatment include the addition of the above-mentioned surface functional groups, the change in contact angle accompanying this, improvement in adhesion, removal of surface contamination, etc., as well as the removal of irregularly shaped objects associated with processing called desmear. There is a surface etching effect such as removal. In particular, since polymer and ceramic are completely different in etching ease, only a polymer having a lower binding energy than ceramic is selectively etched. For this reason, under the gas species and discharge conditions that have an etching action, only the polymer is selectively etched to expose the lubricant (also referred to as particles or filler). In addition to the above plasma treatment, as a means of obtaining an etching effect on the film surface, polishing with a pad including the case of using a chemical solution, brush polishing, polishing with a sponge soaked with a chemical solution, and putting abrasive particles in the polishing pad Examples include polishing with sand, sand blasting, wet blasting, and the like, and these means may be employed together with plasma treatment.

  The plasma treatment may be performed only on one side of the polyimide film or on both sides. When performing plasma treatment on one side, it is possible to perform plasma treatment only on the side of the polyimide film that is not in contact with the electrode by placing the polyimide film in contact with the electrode on one side in the plasma treatment with parallel plate electrodes. it can. If a polyimide film is placed in a state where it is electrically floated in the space between the two electrodes, plasma treatment can be performed on both sides. Moreover, single-sided processing becomes possible by performing plasma processing in the state which stuck the protective film on the single side | surface of the polyimide film. In addition, as a protective film, a PET film with an adhesive or an olefin film can be used.

  It is preferable to perform the acid treatment process which acid-treats the said polyimide film between the said plasma treatment process and the pressurization heat processing process mentioned later to the polyimide film which performed the said plasma treatment. On the polyimide film surface containing the lubricant (particles), even if the lubricant has a convex shape near the surface, a very thin polyimide layer exists on the surface. Since polyimide has strong resistance to acid, even if it is a very thin layer, if polyimide is on the surface of the lubricant, the acid will not be in direct contact with the surface of the lubricant and will not be eroded by the acid treatment. After only the polymer (polyimide) is selectively etched due to the effect, the acid directly contacts the surface of the lubricant. Therefore, if an appropriate acid type is selected and acid treatment is performed, only the lubricant can be obtained in a very short time. Dissolution removal can be performed and a crater is formed.

  This crater is considered to be the remaining part in which the lubricant exposed from the polyimide film surface by the plasma treatment is eluted by the acid, and is not a mere dent but a dent with its edge raised. For reference, FIG. 5 shows an AFM image showing the crater part, FIG. 6 shows a cross-sectional image of the crater part shown in FIG. 5, and FIG. 7 shows an AFM image (10 μm square) including the crater part. The edge portion of the crater is softer than the protrusion in which the lubricant particles are encapsulated, and is deformed with a relatively weak force when the polyimide film and the support are brought into pressure contact. The protrusion containing the lubricant is not easily deformed and inhibits the adhesion between the polyimide film and the support, but the adhesion between the polyimide film and the support is achieved by making the lubricant part into such a crater-like shape. And the peel strength between the polyimide film and the support can be further improved.

  The acid treatment can be performed by immersing the plasma-treated polyimide film in a chemical solution containing acid, or by applying or spraying the chemical solution on the plasma-treated polyimide film. You may use washing together. Moreover, the acid treatment of only one side becomes possible by performing an acid treatment in the state which stuck the protective film on the single side | surface of the polyimide film. As the protective film, a PET film with an adhesive or an olefin film can be used.

As the acid used for the acid treatment, those capable of etching only the lubricant are preferable. For example, HF and BHF having an action of dissolving SiO ₂ and glass are preferably used, and these are usually used as an aqueous solution. For example, since the rate of SiO ₂ etching dissolution in a 10% by mass HF aqueous solution is about 12 cm / sec at room temperature, a SiO ₂ lubricant of about 80 nm can be sufficiently treated by contact with a chemical solution for about 1 minute. Become. Therefore, when acid treatment with an HF aqueous solution or a BHF aqueous solution is performed, it is preferable to use SiO ₂ as a lubricant, but of course, the type of the lubricant is not limited to SiO ₂ .

  As for the acid concentration in a chemical | medical solution, 20 mass% or less is preferable, More preferably, it is 3-10 mass%. If the acid concentration in the chemical solution is too thin, the dissolution rate decreases, so that etching takes time and productivity is lowered. If the acid concentration is too high, the etching time is too short and the chemical solution is exposed to the chemical solution more than necessary.

  The step of adding the plasma treatment and the acid treatment to the polyimide film (raw material) is preferably performed roll-to-roll from the viewpoint of improving the efficiency of the treatment. Since the polyimide film roll subjected to the plasma treatment also has a lubricant, the handling property as a roll is equivalent to that before the plasma treatment. Moreover, after performing plasma treatment with a roll, it is also useful to perform acid treatment after making it into a cut sheet from the viewpoint that simple implementation is possible.

  The surface form of the polyimide film subjected to plasma treatment and acid treatment as described above preferably has a crater having a diameter of 10 to 500 nm on one surface when the surface is observed by an AFM method described later. Ra of 0.3 to 0.95 nm is preferable, and this improves the adhesion, and has a surface to which a smoothness level suitable for bonding and lamination without an adhesive with the support is given. It becomes.

  A polyimide film having a crater having a diameter of 10 to 500 nm on one side has a more appropriate peel strength in bonding lamination without an adhesive with a support. Preferably, the crater has a diameter of 30 to 150 nm. If the diameter of the crater is less than 10 nm, the effect of improving the adhesiveness will be reduced, and if it exceeds 500 nm, excessive etching will be performed, which will adversely affect the strength of the polyimide film and will also have an effect on improving the adhesiveness. It becomes difficult.

  It is particularly preferable that Ra on the other surface of the polyimide film is a smooth surface having a thickness of 0.3 to 0.95 nm in order to produce a precise electric circuit or semiconductor device. For example, when Ra exceeds 2.0 nm. In other words, it does not have the necessary degree of smoothness, and may adversely affect the metal foil film formed thereon in terms of adhesion and smoothness. Such a polyimide film having a smooth surface is produced by using a polyamide acid solution for forming a polyimide (polyimide precursor solution) with a combination of a lubricant and a non-added or a very small amount. In addition, roll roll-up property and proper slipping property at the time of polyimide film production are also given, and the polyimide film production becomes easy.

<Coupling agent treatment>
In the manufacturing method of the laminated body of this invention, the coupling process layer formation process of apply | coating a coupling agent and forming a coupling process layer is performed with respect to the surface of the support body facing the said polyimide film.

  In the present invention, the coupling agent means a compound that is physically or chemically interposed between the support and the polyimide film and has an action of increasing the adhesive force between the two, and is generally a silane coupling. Compounds known as agents, phosphorus coupling agents, titanate coupling agents and the like.

  The coupling agent is not particularly limited, but a silane coupling agent having an amino group or an epoxy group is particularly preferable. Preferable specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltriethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane Hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpro Le) tetrasulfide, 3-isocyanate propyl triethoxysilane, tris - (3-trimethoxysilylpropyl) isocyanurate, chloromethyl phenethyltrimethoxysilane, such as chloromethyl trimethoxysilane.

  As the coupling agent used in the present invention, in addition to the above, for example, 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, butyl 3-mercaptopropionate, 3 -(Dimethoxymethylsilyl) -1-propanethiol, 4- (6-mercaptohexaloyl) benzyl alcohol, 11-amino-1-undecenethiol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoroacetic acid , 2,2 ′-(ethylenedioxy) diethanethiol, 11-mercaptoundecyltri (ethylene glycol), (1-mercaptoundec-11-yl) tetra (ethylene glycol), 1- (methylcarboxy) undeck -11-yl) hexa (ethylene Recall), hydroxyundecyl disulfide, carboxyundecyl disulfide, hydroxyhexadecyl disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, titanium dioctyloxybis (octylene glycolate), zirconium tributoxy monoacetylacetate Nate, zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate and the like can also be used.

  Particularly preferred coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl). -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, amino Phenethyltrimethoxysilane, aminopheny Such as aminomethyl phenethyltrimethoxysilane the like. In the case where particularly high heat resistance is required in the process, it is desirable to use an aromatic group between Si and an amino group.

  As a method of forming a coupling treatment layer by performing a coupling agent treatment, a method of diluting the coupling agent directly or with a solvent, coating and drying the support, heat treatment, or diluting with a coupling agent itself or a solvent, etc. A method of immersing the support in the prepared solution and then drying and heat-treating, a method of adding at the time of polyimide film production, and a treatment with a coupling agent at the same time as polyimide film production can be employed. What is necessary is just to set suitably the application quantity (adhesion amount or content) of a coupling agent so that the film thickness of the coupling process layer formed may become the thickness mentioned later. The conditions for the heat treatment are preferably 50 to 250 ° C., more preferably 75 to 165 ° C., more preferably about 95 to 155 ° C., preferably 30 seconds or more, more preferably 1 minute or more. . If the heating temperature is too high, decomposition or inactivation of the coupling agent may occur, and if it is too low, fixing will be insufficient. Moreover, even if the heating time is too long, the same problem may occur. The upper limit of the heating time is preferably 5 hours, more preferably about 2 hours. In addition, when performing a coupling agent process, since it is known that pH during process will influence a performance large, it is desirable to adjust pH suitably.

<Pattern formation>
In the manufacturing method of the laminated body of this invention, before the below-mentioned pressurization heat processing process, a patterning process is performed to the opposing surface of a polyimide film by an etching, and a predetermined pattern is formed. Thereby, the part with strong peeling strength between a support body and a polyimide film and a weak part can be produced intentionally. The patterning process is, for example, an inactivation process, partial coating, partial removal, partial activation, etc., and preferably an inactivation process. Specifically, a part of the opposing surface of the polyimide film is inactivated. Preferably, it is activated to form a predetermined pattern. Note that patterning a polyimide film means physically removing the polyimide film partially (so-called etching), physically masking the polyimide film microscopically, and chemically modifying the polyimide film. To include.

  As a means to selectively inactivate a part of the opposing surface of the polyimide film to form a predetermined pattern, a part corresponding to the predetermined pattern is temporarily covered or shielded with a mask on the entire surface. Etching or the like may be performed, and then the mask may be removed. If possible, etching may be performed according to a predetermined pattern by a direct drawing method. As a mask, a material generally used as a resist, a photomask, a metal mask or the like may be appropriately selected and used according to an etching method.

  The pattern shape may be appropriately set according to the type of device to be stacked, and is not particularly limited. An example is as shown in FIG. 4. As shown in FIG. 4 (1), the good adhesion portion 11 is arranged only at the outer peripheral portion of the laminate, and the easily peelable portion 12 is arranged inside the laminate. As shown in (2) and (3) of FIG. 4, the pattern in which the good adhesion portion 11 is arranged linearly inside as well as the outer peripheral portion of the laminated body, and (4) of FIG. 4. As shown, there is a pattern in which an annular good adhesion portion 11 is disposed only on the outer peripheral portion of the laminate, and a circular easily peelable portion 12 is disposed inside the laminate.

  As the inactivation treatment, it is preferable to perform at least one selected from the group consisting of blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, actinic radiation irradiation treatment, active gas treatment, and chemical treatment. .

  The blast treatment refers to a treatment in which particles having an average particle diameter of 0.1 to 1000 μm are sprayed on an object together with gas or liquid. In the present invention, it is preferable to use blasting using particles having a small average particle diameter as much as possible.

  The vacuum plasma treatment refers to a treatment in which an object is exposed to plasma generated by discharge in a decompressed gas, or ions generated by the discharge collide with the object. As the gas, neon, argon, nitrogen, oxygen, carbon fluoride, carbon dioxide, hydrogen or the like alone or a mixed gas can be used.

  The atmospheric pressure plasma treatment is a treatment in which an object is exposed to plasma generated by a discharge generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge collide with the object. say. As the gas, neon, argon, nitrogen, oxygen, carbon dioxide, hydrogen or the like alone or a mixed gas can be used.

  The corona treatment refers to a treatment in which an object is exposed to a corona discharge atmosphere generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge collide with the object.

  The actinic radiation irradiation treatment refers to a treatment for irradiation with radiation such as electron beam, alpha ray, X-ray, beta ray, infrared ray, visible ray, ultraviolet ray, laser beam irradiation treatment. In addition, when performing a laser beam irradiation process, it becomes easy to process especially by a direct drawing system. In this case, even a visible light laser has much larger energy than general visible light, and therefore can be treated as a kind of actinic radiation in the present invention.

  The active gas treatment is a gas having an activity that causes chemical or physical change at least on the opposite surface of the polyimide film, such as halogen gas, hydrogen halide gas, ozone, high concentration oxygen gas, ammonia, organic alkali, A treatment that exposes an object to a gas such as an organic acid.

  The above chemical treatment is intended for a liquid having an activity that causes a chemical or physical change at least on the opposite surface of the polyimide film, such as an alkaline solution, an acid solution, a reducing agent solution, an oxidizing agent solution, or a solution. A treatment that exposes an object.

  In particular, from the viewpoint of productivity, as the inactivation treatment, a method combining actinic radiation and a mask or a method combining an atmospheric pressure plasma treatment and a mask is preferably used. The actinic radiation treatment is preferably an ultraviolet irradiation treatment, that is, a UV irradiation treatment from the viewpoint of economy and safety, and will be described in detail below.

  In the present invention, the UV irradiation treatment is a treatment in which a polyimide film is placed in a device that generates ultraviolet light (UV light) having a wavelength of 400 nm or less (UV light), and the UV light wavelength is preferably 260 nm or less. More preferably, the short wavelength is 200 nm or less. When such UV light having a short wavelength is irradiated in an environment where oxygen exists, UV light energy is added to the polyimide film, and active oxygen and ozone in an excited state are generated in the vicinity of the sample. The inactivation treatment of the opposing surface of the film can be performed more effectively. However, at a wavelength of 170 nm or less, absorption of UV light by oxygen is remarkable, so that it is necessary to consider the UV light reaching the polyimide film. Irradiation in a completely oxygen-free atmosphere does not show the effect of surface modification (inactivation) with active oxygen or ozone, so it must be devised to allow active oxygen and ozone to reach while UV light passes. . For example, a device that puts a UV light source in a nitrogen atmosphere and transmits UV light through quartz glass, shortens the distance from the quartz glass to the polyimide film, and suppresses UV light absorption. In addition, the method of controlling the absorption of UV light by controlling the amount of oxygen instead of the normal atmosphere, the control of the gas flow between the UV light source and the coupling treatment layer, etc. It is effective as a method for controlling the amount of generation.

The irradiation intensity of UV light is preferably 5 mW / cm ² or more when measured using an ultraviolet light meter having a sensitivity peak in a wavelength range of at least 150 nm to 400 nm, and 200 mW / cm ² or less is for preventing alteration of the support. This is desirable. The irradiation time of UV light is preferably 0.1 minutes or more and 30 minutes or less, more preferably 0.5 minutes or more, still more preferably 1 minute or more, particularly preferably 2 minutes or more, and more preferably 10 minutes or less. More preferably, it is 5 minutes or less, and particularly preferably 4 minutes or less. In terms of integrated light quantity is preferably ^{30mJ / cm 2 ~360000mJ / cm 2} , more preferably ^{300mJ / cm 2 ~120000mJ / cm 2} , more preferably from ^{600mJ / cm 2 ~60000mJ / cm 2} .

  Pattern formation during the UV irradiation process is performed by intentionally creating a portion that irradiates light and a portion that does not irradiate light. As a method of forming a pattern, a method of making a portion that shields UV light and a portion that does not shield UV light, a method of scanning UV light, or the like can be given. In order to clarify the end of the pattern, it is effective to block the UV light and cover the polyimide film with a mask. It is also effective to scan with a parallel beam of a UV laser.

  The light source that can be used for UV irradiation treatment is not particularly limited. , Ar laser, D2 lamp and the like. Among these, excimer lamps, low-pressure mercury lamps, Xe excimer lasers, ArF excimer lasers, KrF excimer lasers, and the like are preferable.

  In addition, in the manufacturing method of the laminated body of this invention, it opposes the polyimide film in a coupling process layer by an etching together with the pattern formation process to the opposing surface of a polyimide film before the pressurization heat processing process mentioned later. A predetermined pattern can also be formed on the side surface. The formation of the predetermined pattern refers to creating a region where the coating amount of the coupling agent, the activity of the surface activation treatment, and the like are intentionally manipulated. Thus, by performing pattern formation of the coupling treatment layer and treating the surface of the coupling treatment layer, it is possible to remove contamination from the surface of the silane coupling treatment layer unlike ordinary cleaning. Affixing failure due to contamination on the surface of the coupling agent layer is less likely to occur, and the surface of the coupling agent layer has no irregularities, so that the film can be successfully applied to the film.

  As a pattern formation method, a method of manipulating the coating amount of the coupling agent using a mask prepared in a predetermined pattern in advance when applying the coupling agent can be exemplified. It is also possible to perform patterning by irradiating the surface to which the coupling agent is applied with active energy rays and using a technique such as masking or scanning in combination. Here, the active energy ray irradiation means the operation of irradiating energy rays such as ultraviolet rays, electron rays, X-rays, etc., and ozone gas generated near the irradiated surface simultaneously with the ultraviolet ray irradiation light effect as in the ultraviolet ray irradiation treatment of an extremely short wavelength. Include gas exposure effects. In addition to these, patterning can also be performed by corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, sandblast treatment, or the like.

The polyimide film that has been deactivated as described above has a good adhesion portion that is a portion where the peel strength between the support and the polyimide film is strong, depending on whether the polyimide film has been deactivated (etched), and the support. A pattern composed of an easily peelable portion which is a portion having a weak peel strength from the polyimide film is formed. By performing the patterning process in the UV irradiation part, the polyimide becomes rather unstable and the adhesive strength between the entire polyimide film and the coupling layer is rather lowered. For example, when performing a UV / O ₃ treatment on the polyimide surface, for UV / O ₃ treatment is a surface treatment is oxidation proceeds, bonds of the polyimide is destroyed by the progress of oxidation, unstable bond the entire polyimide film A weak layer is formed and a part is removed. For this reason, even if it adhere | attaches on this layer, the adhesive force with the whole polyimide film is low. Therefore, when UV / O ₃ treatment is performed on the polyimide film surface, the UV irradiated portion becomes an easily peelable portion, while the UV non-irradiated portion becomes a good bonded portion having a strong peel strength. Further, when UV / O ₃ treatment is performed on the surface of the coupling treatment layer, when the coupling treatment layer is a silane coupling treatment layer, oxidation proceeds, so that organic components having an adhesion function are removed, but SiO 2 is removed. ₂ is considered to remain. Since OH groups are also generated, this layer becomes a surface capable of hydrogen bonding. Therefore, even when the UV / O ₃ treatment is performed on the surface of the coupling treatment layer, the UV irradiated portion becomes an easily peeled portion, and the UV non-irradiated portion becomes a good bonded portion having a strong peel strength.

  When the silane coupling agent layer is irradiated with UV, the heat-resistant peel strength is higher than the peel strength of the UV-irradiated part. However, when the polyimide film is irradiated with UV, the heat-resistant peel strength is peeled off from the UV-irradiated part. It can be lower than the strength. About a heat-resistant peeling strength and the peeling strength of a UV irradiation part, a measuring method is explained in full detail in an Example.

  It is industrially advantageous to use glass as the substrate as the support. In this case, it is more practical to reduce the peel strength by UV irradiation, but depending on the application, the substrate used, and the required peel strength It is also conceivable that the UV light irradiated portion is a good adhesion portion.

<Pressurized heat treatment>
The laminated body of the present invention includes a pressure heat treatment step in which the support and the polyimide film provided with the coupling treatment layer are superposed and pressure heat treated after the coupling treatment layer formation step and the pattern formation step. It is produced by performing.

  The pressure heat treatment may be performed while heating a press, a laminate, a roll laminate, or the like, for example, in an atmospheric pressure atmosphere or in a vacuum. A method of heating under pressure in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, press or roll lamination in an air atmosphere is preferable, and a method using rolls (roll lamination or the like) is particularly preferable.

  The pressure during the pressure heat treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be damaged. If the pressure is too low, a non-adhering part may be produced, resulting in insufficient adhesion. The temperature during the pressure heat treatment is 150 ° C to 400 ° C, more preferably 250 ° C to 350 ° C. If the temperature is too high, the polyimide film may be damaged. If the temperature is too low, the adhesion tends to be weak.

  The pressure heat treatment can be performed in an atmospheric pressure atmosphere as described above. However, in order to obtain a stable peel strength on the entire surface, it is preferably performed under vacuum. At this time, the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.

  As an apparatus that can be used for the pressure heat treatment, for example, “11FD” manufactured by Imoto Seisakusho Co., Ltd. can be used to perform pressing in a vacuum, and a roll film laminator or a vacuum in vacuum can be used. For example, “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used for vacuum lamination such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.

  The pressure heat treatment can be performed separately in a pressure process and a heating process. In this case, first, the polyimide film and the support are pressurized (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, a temperature of less than 120 ° C., more preferably 95 ° C. or less) to ensure adhesion between the two. Thereafter, at a low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or a relatively high temperature at normal pressure (for example, 120 ° C. or more, more preferably 120 to 250 ° C., further preferably 150 to 230 ° C.). By heating with, the chemical reaction at the adhesion interface is promoted and the polyimide film and the support can be laminated.

  In general, as a method of obtaining a laminate of a support and a polyimide film, a method in which a polyimide varnish (polyamic acid solution described above) is directly applied on the support and imidized to form a film is also considered. In the invention, the polyimide is formed into a film and then laminated on the support. For example, when a polyamic acid solution is imidized by heating on a support, for example, although it depends on the support, a concentric film thickness distribution can be easily formed, and the state of the front and back of the polyimide film (transfer of heat) This is because the film tends to be warped or lifted from the support due to the difference in the method, etc., whereas these problems can be avoided if the film is formed in advance. Furthermore, by superimposing the film on the support, it is also possible to form a device (circuit or the like) on the film before superposition within a range where pressure heat treatment can be performed.

<Application>
In the method for producing a laminate of the present invention, as an application example, a polyimide film in the laminate or a hole portion penetrating in the film thickness direction of the entire laminate is provided as necessary, thereby providing a non-polyimide portion. Also good. The part is not particularly limited, but is preferably filled with a metal whose main component is a metal such as Cu, Al, Ag, Au, or formed by a mechanical drill or laser drilling. And a hole in which a metal film is formed on the wall surface of the hole by sputtering, electroless plating seed layer formation, or the like.

(Laminate)
The laminate of the present invention is a laminate in which a support and a polyimide film are laminated via a coupling treatment layer, and a good adhesion portion having a different peel strength between the support and the polyimide film and an easy adhesion portion. The good adhesion part and the easy peeling part form a predetermined pattern. Thereby, after producing a device on a polyimide film without peeling even in a high temperature process at the time of device production, it becomes a laminated body which can peel a polyimide film from a support easily. The laminate of the present invention can be obtained by the method for producing a laminate of the present invention, and details of the support, the polyimide film, the coupling treatment layer and the like are as described above.

  In the present invention, the well-bonded portion and the easily peelable portion are formed by changing the surface properties depending on the presence or absence of an inactivation treatment such as UV light irradiation. That is, the good adhesion portion in the present invention is a portion that has not been subjected to inactivation treatment such as UV light irradiation, and refers to a portion where the peel strength between the support and the polyimide film is strong. The easy peeling part in this invention is a part to which inactivation processes, such as UV light irradiation, were given, and point out a part with weak peeling strength of a support body and a polyimide film.

  In the present invention, the 180-degree peel strength between the support and the polyimide film may be appropriately set according to the type and process of the device laminated thereon, and is not particularly limited. The 180-degree peel strength is preferably 1/2 or less, more preferably 1/5 or less of the 180-degree peel strength of the good adhesion portion. As a general theory, the 180 degree peel strength of the good adhesion portion is preferably 0.5 N / cm or more and 5 N / cm or less, more preferably 0.8 N / cm or more and 2 N / cm or less. The 180 degree peel strength of the easy peel portion is preferably 0.01 N / cm or more and 0.4 N / cm or less, more preferably 0.01 N / cm or more and 0.2 N / cm or less. Here, the lower limit of the 180-degree peel strength of the easily peelable portion is a value that takes into account the bending energy of the polyimide film. 180 degree peel strength in this invention can be measured by the method mentioned later in an Example. In addition, the heat-resistant peel strength, acid peel strength, and alkali peel strength, which will be described later in the examples, are preferably 0.5 N / cm or more and 5 N / cm or less, respectively. It can happen.

(Device structure manufacturing method)
The method for producing a device structure of the present invention is a method for producing a structure in which a device is formed on a polyimide film as a substrate, using the laminate of the present invention having a support and a polyimide film. .

  In the manufacturing method of the device structure of the present invention, after forming a device on the polyimide film of the laminate produced by the method described above, the polyimide film is cut into the polyimide film of the easy peelable portion of the laminate. Is peeled from the support.

  As a method of cutting the polyimide film of the easy-release part of the laminate, a method of cutting the polyimide film with a cutting tool such as a blade, or a method of cutting the polyimide film by relatively scanning the laser and the laminate There are a method of cutting the polyimide film by relatively scanning the water jet and the laminate, a method of cutting the polyimide film while cutting slightly to the glass layer with a semiconductor chip dicing device, etc., but the method is particularly limited. It is not a thing. For example, in adopting the above-described method, it is possible to appropriately employ a technique such as superimposing ultrasonic waves on the cutting tool or adding a reciprocating operation or an up-and-down operation to improve the cutting performance.

  When making a cut in the polyimide film of the easy-peeling portion of the laminate, the position where the cut is made only needs to include at least a part of the easy-peeling portion, and is basically cut according to a pattern. However, if an attempt is made to accurately cut according to the pattern at the boundary between the good adhesion portion and the easy peeling portion, an error also occurs. Therefore, it is preferable to cut slightly to the easy peeling portion side from the pattern in terms of increasing productivity. Moreover, in order to prevent peeling without permission before peeling, there may be a production system that cuts into the bonded portion slightly better than the pattern. Furthermore, if the width of the good adhesion portion is set narrow, the polyimide film remaining in the good adhesion portion at the time of peeling can be reduced, the use efficiency of the film is improved, and the device area with respect to the laminate area is large. Thus, productivity is improved. Furthermore, an easy peeling part is provided in a part of the outer peripheral part of the laminated body, and the method in which the outer peripheral part is used as a cutting position and actually peeled off without making a cut is also an extreme form of the present invention. Yeah.

  The method of peeling the polyimide film from the support is not particularly limited, but is a method of rolling from the end with tweezers, etc., and sticking an adhesive tape to one side of the cut portion of the polyimide film with a device, and then rolling from the tape portion. A method, a method in which one side of a cut portion of a polyimide film with a device is vacuum-adsorbed and then wound from that portion can be employed. In the case of peeling, if a bend with a small curvature occurs in the cut portion of the polyimide film with the device, stress may be applied to the device in that portion and the device may be destroyed. It is desirable to remove. For example, it is desirable to roll while winding on a roll having a large curvature, or to roll using a machine having a configuration in which the roll having a large curvature is located at the peeling portion.

  In addition, the reinforcing member can be fixed before the device structure (polyimide film with a device) of the present invention is a final product. In this case, the reinforcing member may be fixed after being peeled off from the support, but after fixing the reinforcing member, the polyimide film is cut off and peeled off from the support, or the polyimide film is cut into It is preferable that the reinforcing member is fixed to the cut portion and then peeled off. In the case where the reinforcing member is fixed before peeling, it is possible to make the device part less susceptible to stress by considering the elastic modulus and film thickness of the polyimide film and the reinforcing member. For example, a PET film with an adhesive is attached as a reinforcing member only to the easily peelable portion of the laminate of the present invention, and a device with a device is formed by cutting the easy peelable portion with the adhesive PET film attached. The polyimide film may be peeled off, or a PET film with an adhesive is attached to the entire laminate of the present invention as a reinforcing member, and an easy-peeled portion of the laminate is cut to provide an PET film with an adhesive. You may make it peel a polyimide film with a device in the stuck state.

  When the reinforcing member is fixed before peeling, a polymer film, ultrathin glass, SUS, or the like is preferably used as the reinforcing member. The polymer film has an advantage that the lightness of the device is maintained, and further includes transparency, various workability, and difficulty in cracking. Ultra-thin glass has the advantages of providing gas barrier properties, chemical stability, and transparency. SUS has the advantage that it can be shielded electrically and is difficult to break. In addition, since it is after passing the process which already requires high temperature as a polymer film, there are few restrictions of heat resistance, and various polymer films can be selected. These reinforcing members can be fixed by adhesion or adhesion.

In the present invention, a method for forming a device on a polyimide film as a substrate may be appropriately performed according to a conventionally known method. In addition, the glass with the polyimide film attached may be cleaned before the device is manufactured. By wet cleaning immediately before the device is manufactured, atmospheric pressure plasma treatment, vacuum plasma treatment, or the above UV / O ₃ treatment. What is necessary is just to perform suitably according to conventionally well-known methods, such as washing | cleaning.

  The device in the present invention is not particularly limited, and examples thereof include only electronic circuit wiring, electrical resistance, passive devices such as coils and capacitors, active devices including semiconductor elements, and electronic circuit systems that combine these devices. is there. Examples of the semiconductor element include a solar cell, a thin film transistor, a MEMS element, a sensor, and a logic circuit.

  For example, in a film-like solar cell using the laminate of the present invention, a laminate X including a photoelectric conversion layer made of a semiconductor is formed on the base material of the polyimide film of the laminate of the present invention. . This laminated body X has a photoelectric conversion layer that converts sunlight energy into electric energy as an essential component, and usually further includes an electrode layer for taking out the obtained electric energy.

  Hereinafter, a laminated structure in which a photoelectric conversion layer is sandwiched between a pair of electrode layers will be described as a typical example of the laminate X formed to constitute a film-like solar cell. However, a structure in which several photoelectric conversion layers are stacked can be said to be a solar cell of the present invention if it is produced by PVD or CVD. Of course, the laminated structure of the laminated body X is not limited to the embodiment described below, and the structure of the laminated body of the solar cell of the prior art may be appropriately referred to, and a protective layer and known auxiliary means may be added. It ’s good.

One electrode layer (hereinafter also referred to as a back electrode layer) of the pair of electrode layers is preferably formed on one main surface of the polyimide film substrate. The back electrode layer is obtained by laminating a conductive inorganic material by a conventionally known method, for example, a CVD (chemical vapor deposition) method or a sputtering method. Examples of the conductive inorganic material include metal thin films such as Al, Au, Ag, Cu, Ni, and stainless steel, In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ and Sn ₂ O Oxide semiconductor-based conductive materials such as those to which ₃ is added). Preferably, the back electrode layer is a metal thin film. The thickness of the back electrode layer is not particularly limited, and is usually about 30 to 1000 nm. Alternatively, a film forming method that does not use a vacuum, such as Ag paste, may be employed for extracting some electrodes.

The photoelectric conversion layer for converting the energy of sunlight into electric energy is a layer made of a semiconductor, and CuInSe ₂ which is a compound semiconductor thin film (chalcopyrite structure semiconductor thin film) made of a group I element, a group III element, and a group VI element. A (CIS) film, or a Cu (In, Ga) Se ₂ (CIGS) film (hereinafter, collectively referred to as a CIS film) in which Ga is dissolved, and a layer made of a silicon-based semiconductor. Examples of the silicon-based semiconductor include a thin film silicon layer, an amorphous silicon layer, and a polycrystalline silicon layer. The photoelectric conversion layer may be a laminate having a plurality of layers made of different semiconductors. Moreover, the photoelectric converting layer using a pigment | dye may be sufficient. Further, an organic thin film semiconductor made of an organic compound such as a conductive polymer or fullerene may be used.

  The thin film silicon layer is a silicon layer obtained by a plasma CVD method, a thermal CVD method, a sputtering method, a cluster ion beam method, a vapor deposition method, or the like.

  The amorphous silicon layer is a layer made of silicon having substantially no crystallinity. The lack of crystallinity can be confirmed by not giving a diffraction peak even when irradiated with X-rays. Means for obtaining an amorphous silicon layer are known, and examples of such means include a plasma CVD method and a thermal CVD method.

  The polycrystalline silicon layer is a layer made of an aggregate of microcrystals made of silicon. The above amorphous silicon layer is distinguished by giving a diffraction peak by irradiation with X-rays. Means for obtaining a polycrystalline silicon layer are known, and such means include means for heat-treating amorphous silicon.

  The photoelectric conversion layer is not limited to a silicon-based semiconductor layer, and may be, for example, a thick film semiconductor layer. The thick film semiconductor layer is a semiconductor layer formed from a paste such as titanium oxide, zinc oxide, or copper iodide.

As a means for configuring the semiconductor material as the photoelectric conversion layer, a known method may be adopted as appropriate. For example, an about 20 nm a-Si (n layer) is formed by performing high-frequency plasma discharge in a gas in which phosphine (PH ₃ ) is added to SiH ₄ at a temperature of 200 to 500 ° C., and subsequently SiH _4. An a-Si (i layer) of about 500 nm can be formed only with gas, and then diborane (B ₂ H ₆ ) can be added to SiH ₄ to form a p-Si (p layer) of about 10 nm.

Of the pair of electrode layers sandwiching the photoelectric conversion layer, an electrode layer (hereinafter also referred to as a current collecting electrode layer) provided on the side opposite to the polyimide film substrate is formed by consolidating a conductive paste containing a conductive filler and a binder resin. The electrode layer may be a transparent electrode layer. As the transparent electrode layer, an oxide semiconductor material such as In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ added with Sn) can be preferably used.

  Thus, a film-like solar cell in which transparent electrode / p-type a-Si / i-type a-Si / n-type a-Si / metal electrode / polyimide film are laminated in this order, which is a preferred embodiment of the present invention. can get. Alternatively, the p layer may be a-Si, the n layer may be polycrystalline silicon, and a thin undoped a-Si layer may be inserted between them. In particular, when an a-Si / polycrystalline silicon hybrid type is used, the sensitivity to the sunlight spectrum is improved. In manufacturing a solar cell, an antireflection layer, a surface protective layer, or the like may be added in addition to the above structure.

  The thin film transistor (TFT) refers to a semiconductor layer in which a transistor and an insulating film, an electrode, a protective insulating film, and the like that form an element are formed by depositing a thin film. It is usually distinguished from silicon wafers that use silicon as the semiconductor layer. Usually, a thin film is produced by a technique using a vacuum such as PVD (physical vapor deposition) such as vacuum vapor deposition or CVD (chemical vapor deposition) such as plasma CVD. For this reason, what is not a single crystal like a silicon wafer is included. Even if Si is used, microcrystalline silicon TFT, high-temperature polysilicon TFT, low-temperature polysilicon TFT, oxide semiconductor TFT, organic semiconductor TFT, and the like are included.

  The above-mentioned MEMS element means an object manufactured using MEMS technology, and includes an inkjet printer head, a probe for a scanning probe microscope, a contactor for an LSI prober, an optical spatial modulator for maskless exposure, an optical integrated element, an infrared ray This includes sensors, flow sensors, acceleration sensors, MEMS gyro sensors, RF MEMS switches, internal and external blood pressure sensors, and video projectors using grating light valves and digital micromirror devices.

  The above sensors include strain gauges, load cells, semiconductor pressure sensors, optical sensors, photoelectric elements, photodiodes, magnetic sensors, contact temperature sensors, thermistor temperature sensors, resistance thermometer temperature sensors, and thermocouple temperature sensors. Non-contact temperature sensor, radiation thermometer, microphone, ion concentration sensor, gas concentration sensor, displacement sensor, potentiometer, differential transformer displacement sensor, rotation angle sensor, linear encoder, tachometer generator, rotary encoder, optical position sensor (PSD) ), Ultrasonic distance meter, capacitance displacement meter, laser Doppler vibrometer, laser Doppler velocimeter, gyro sensor, acceleration sensor, earthquake sensor, one-dimensional image / linear image sensor, two-dimensional image / CCD image Sensor, CMOS image sensor, liquid / leak sensor (leak sensor), liquid sensor (level sensor), hardness sensor, electric field sensor, current sensor, voltage sensor, power sensor, infrared sensor, radiation sensor, humidity sensor, odor sensor , Flow sensor, tilt sensor, vibration sensor, time sensor, composite sensor that combines these sensors, sensors that output other physical quantities or sensitivity values based on some calculation formula from the values detected by these sensors, etc. Including.

  The logic circuit includes a logic circuit based on NAND and OR and a circuit synchronized by a clock.

  About the manufacturing method of the laminated body of this invention explained in full detail above, and the manufacturing method of the device structure of this invention, when each example of one embodiment is demonstrated using drawing, it is as showing in FIGS. 1-3. .

  FIG. 1 is a schematic view showing an embodiment of a method for producing a laminate according to the present invention, in which (1) shows a glass substrate 1 and (2) shows that a coupling agent is applied on the glass substrate 1 and dried. The step of forming the coupling treatment layer 2 is shown. (3) shows the step of irradiating the UV light after the UV light blocking mask 3 is placed on the polyimide film 4, and (4) shows the step of irradiating the UV light. The stage where the light blocking mask 3 is removed is shown. Here, in the polyimide film 4, the UV exposure part is the UV irradiation part 5, and the remaining part is the UV non-irradiation part 6. (5) shows a stage where the polyimide film 4 is pasted on the coupling treatment layer 2, and (6) shows a cut in the polyimide film 4 on the UV irradiation unit 5, and a part 7 of the polyimide film is removed from the glass substrate 1. The stage which peeled is shown.

  FIG. 2 is a schematic view showing one embodiment of the method for producing a device structure of the present invention, and (1) to (5) are the same as FIG. (6) shows a stage in which the gas barrier layer 8 is laminated on the surface opposite to the surface irradiated with UV on the polyimide film 4, and (7) shows a stage in which the device 9 is fabricated on the surface of the gas barrier layer 8 on the UV irradiation section. (8) shows a stage where the polyimide film 4 on the UV irradiation unit 5 is cut and a part 7 ′ of the polyimide film is peeled off from the glass substrate 1.

  FIG. 3 is a schematic view showing another embodiment of the device structure manufacturing method of the present invention, and (1) to (4) are the same as FIG. (5) shows a stage in which the UV light blocking mask 3 ′ is placed on the coupling treatment layer 2 and then irradiated with UV light, and (6) shows a stage in which the UV light blocking mask 3 ′ is removed after the UV light irradiation. Is shown. Here, in the coupling processing layer 2, the UV exposure part is the UV irradiation part 5 ', and the remaining part is the UV non-irradiation part 6'. (7) shows the stage where the polyimide film 4 is affixed on the coupling treatment layer 2, and (8) shows the stage where the gas barrier layer 8 is laminated on the surface opposite to the UV-irradiated surface on the polyimide film 4. (9) shows a stage in which the device 9 is produced on the surface of the gas barrier layer 8 on the UV irradiation part, and (10) shows a notch in the polyimide film 4 on the UV irradiation part 5 and a part 7 ″ of the polyimide film. The stage which peeled from the glass substrate 1 is shown.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

  The physical property evaluation methods in the following examples are as follows.

<Thickness of polyimide film>
The thickness of the polyimide film was measured using a micrometer (“Millitron 1245D” manufactured by FineLuf).

<Tension modulus, tensile strength and tensile elongation at break of polyimide film>
From the polyimide film to be measured, strip-shaped test pieces each having a flow direction (MD direction) and a width direction (TD direction) of 100 mm × 10 mm were cut out, and a tensile tester (“Autograph (registered trademark)” manufactured by Shimadzu Corporation) was cut out. ); Model name AG-5000A "), and the tensile modulus, tensile strength, and tensile elongation at break were measured in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm.

<Peel strength>
The peel strength (180 degree peel strength) was measured under the following conditions according to the 180 degree peel method described in JIS C6471. In addition, in the sample used for this measurement, a non-adhesive portion of the polyimide film is provided on one side by designing the size of the polyimide film to 110 mm × 200 mm with respect to a □ 100 mm support (glass). "Shiro".
Device name: “Autograph AG-IS” manufactured by Shimadzu Corporation
Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Air Measurement sample width: 1 cm

(1) Peel strength of UV non-irradiated part For measuring the peel strength of the UV non-irradiated part, a laminate produced separately in the same manner as in each of the examples and comparative examples was used except that UV irradiation was not performed.
(2) Peeling strength of UV irradiated part The peeling strength of the UV irradiated part was measured on the UV irradiated part of the laminate subjected to UV irradiation.
(3) Heat-resistant peel strength The heat-resistant peel strength was measured by placing the laminate subjected to UV treatment in a muffle furnace in a nitrogen atmosphere, heating it to 400 ° C. at a rate of temperature increase of 10 ° C./min, and directly at 400 ° C. After holding for 1 hour, the sample obtained by opening the door of the muffle furnace and allowing to cool in the atmosphere was used.
(4) Peel strength after PCT (saturated pressurized steam test) The laminate after 96 hours in an environment of saturated steam, 2 atm and 121 ° C is taken out into the atmosphere, and the peel strength is measured in an environment of room temperature and atmospheric pressure. The peel strength after PCT was used.
(5) Post-IPA (Isopropyl Alcohol) Peeling Strength Measurement of post-IPA peeling strength was performed using a sample obtained by immersing in isopropyl alcohol at room temperature (23 ° C.) for 30 minutes, washing with water three times, and air-drying. went.
(6) Acid peel strength The acid peel strength was measured by immersing the laminate (laminated with UV irradiation) in an 18% by mass hydrochloric acid solution at room temperature (23 ° C) for 30 minutes and washing with water three times. And then using a sample obtained by air drying.
(7) Alkali Resistance Peel Strength Measurement of alkali resistance peel strength was performed by using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution (room temperature (23 ° C.)) for the laminate (laminated body subjected to UV irradiation). For 30 minutes, washed with water three times and then air-dried.

<Lubricant particle size>
The particle size of the lubricant (silica) used in each production example is in a state of dispersion in a solvent (dimethylacetamide), using a laser scattering particle size distribution analyzer “LB-500” manufactured by Horiba Ltd. The particle size distribution was determined, and the volume average particle size was calculated.

<Linear expansion coefficient (CTE) of polyimide film>
About the flow direction (MD direction) and the width direction (TD direction) of the polyimide film to be measured, the expansion / contraction rate is measured under the following conditions, and intervals of 15 ° C. (30 ° C. to 45 ° C., 45 ° C. to 60 ° C., ... ) Was measured up to 300 ° C., and the average value of all measured values measured in the MD and TD directions was calculated as the coefficient of linear expansion (CTE).
Device name: “TMA4000S” manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rising start temperature: 30 ° C
Temperature rise end temperature; 300 ° C
Temperature increase rate: 5 ° C./min Atmosphere: Argon initial load: 34.5 g / mm ²

<Ra value of polyimide film surface>
The Ra value (surface morphology) on the surface of the polyimide film was measured using a scanning probe microscope with a surface physical property evaluation function (“SPA300 / nanonavi” manufactured by SII Nanotechnology). The measurement is performed in DFM mode, the cantilever is “DF3” or “DF20” manufactured by SII Nanotechnology, the scanner is “FS-20A” manufactured by SII Nanotechnology, and the scanning range is 10 μm square. And the measurement resolution was 512 × 512 pixels. After correcting the quadratic tilt with the software attached to the device for the measurement image, if noise accompanying the measurement is included, other flattening processing (for example, flat processing) is used as appropriate, and Ra with the software attached to the device is used. The value was calculated. Measurement was performed at arbitrary three locations to determine the Ra value, and an average value thereof was adopted.

<Number of craters and crater diameter on polyimide film surface>
Measurement was performed by the following AFM method. That is, the number of craters on the surface of the polyimide film was measured using a scanning probe microscope with a surface property evaluation function (“SPA300 / nonavivi” manufactured by SII Nanotechnology). The measurement is performed in DFM mode, the cantilever is “DF3” or “DF20” manufactured by SII Nanotechnology, the scanner is “FS-20A” manufactured by SII Nanotechnology, and the scanning range is 10 μm square. And the measurement resolution was 1024 × 512 pixels. After the quadratic tilt correction was performed on the measurement image using the software attached to the apparatus, the crater portion was observed. As shown in FIG. 8, the crater has a shape in which the center of the convex part rising from the flat part is depressed. Therefore, the diameter of the cross section (the distance between the maximum heights) at the position of the maximum height of the swell was defined as the crater diameter ((1) in FIG. 8 represents the height of the unevenness of the polyimide film in shades of color. It is a figure (a position where white is high, a position where black is low), (2) is a cross-sectional display example of the unevenness of the polyimide film in the white line part of (1), and (3) shows the crater diameter). And it measured about arbitrary three crater parts, the crater diameter was calculated | required, and those average values were employ | adopted.

  The number of craters was measured by analyzing the obtained 10 μm square measurement image (AFM image) with image processing software “ImageJ”. “ImageJ” is an open source public domain image processing software developed by the National Institutes of Health (NIH). Specifically, first, a binarization operation is performed in which a part is classified into a part having a higher position and a part having a lower position according to a certain threshold (see (2) and (3) in FIG. 9). At this time, as a threshold value, a position that is 12% higher than the particle size of the lubricant used from the maximum point of the distribution with respect to the information in the height direction of the AFM image (a position that is 10 nm higher when the diameter of the lubricant is 80 nm). A threshold was used. By this binarization, an image of only black and white (see (3) in FIG. 9) was obtained, and the number of ring-shaped portions therein was obtained by image processing. In other words, the recognition of the annular shape is performed by performing an operation of filling the enclosed circle, and reversing the image filled in the circle (see (4) of FIG. 9) and the image not filled ((( 5) and the image logical product (see (6) of FIG. 9) can be extracted, so that only the inside of the ring can be extracted ((1) in FIG. It is the figure (the position where white is high, the position where black is low) represented by shading, (2) is a cross-sectional display example (straight line is a threshold value) of the unevenness of the polyimide film of the white line part of (1), (3) Is an example of binarization with a threshold value, (4) is an example in which the annular portion is filled, (5) is an example in which (3) is inverted, and (6) is (4) And (5)). The number of craters was calculated by counting craters with a diameter of 10 to 500 nm from the image logical product image obtained by this operation. And it measured about arbitrary three places, calculated | required the number of craters, and employ | adopted those average values.

<Thickness of coupling layer>
The thickness (nm) of the coupling treatment layer (SC layer) was prepared by separately preparing a sample obtained by applying and drying a coupling agent on a cleaned Si wafer in the same manner as in each example and comparative example, About the film thickness of the coupling process layer formed on this Si wafer, it measured by the ellipsometry method on condition of the following using the spectroscopic ellipsometer ("FE-5000" by Photo company).
Reflection angle range: 45 ° to 80 °
Wavelength range: 250 nm to 800 nm
Wavelength resolution: 1.25 nm
Spot diameter: 1mm
tan Ψ; Measurement accuracy ± 0.01
cosΔ; Measurement accuracy ± 0.01
Measurement: Method Rotating analyzer method Deflector angle: 45 °
Incident angle: 70 ° fixed Analyzer: 0-360 ° in 11.25 ° increments
Wavelength: 250 nm to 800 nm
The film thickness was calculated by fitting by a non-linear least square method. At this time, the model is Air / thin film / Si,
n = C3 / λ4 + C2 / λ2 + C1
k = C6 / λ4 + C5 / λ2 + C4
The wavelength dependence C1 to C6 was determined by the following formula.

<Evaluation of polyimide film: slipperiness>
Two polyimide films are overlapped on different surfaces (that is, not on the same surface but on the wound outer surface and the wound inner surface when wound as a film roll), and the overlapped polyimide film is sandwiched between the thumb and forefinger, When lightly rubbed, the case where the polyimide film and the polyimide film slip was evaluated as “◯”, and the case where it did not slip was evaluated as “x”. In addition, although it may not slip on winding outer surfaces or between winding inner surfaces, this is not made into an evaluation item.

<Evaluation of polyimide film: roll winding property>
When a long polyimide film is wound on a winding roll (outer diameter of the mandrel: 15 cm) at a speed of 2 m / min, “皺” indicates that wrinkles do not occur and smooth winding is possible. A case where wrinkles occurred partially was evaluated as “Δ”, and a case where wrinkles occurred or a case where winding was not possible due to winding around a roll was evaluated as “x”.

<Glass transition temperature>
Using a DSC differential thermal analyzer, the glass transition temperature of the polyimide film was determined from the presence or absence of heat absorption / dissipation due to structural changes in the range from room temperature to 500 ° C. No glass transition temperature was observed in any of the polyimide films.

<Floating density in laminate>
Samples of 200 × 200 mm were prepared, and the number of floats was counted for four regions of 100 × 100 mm. Specifically, the number of floats having a major axis of 1 mm or more among the floats between the glass and the polyimide film viewed from the glass surface side was counted in 4 regions. Then, the number of floats in the four regions was averaged (the total number of floats in the 200 × 200 mm sample was divided by 4) to obtain the float density in the laminate.

(Preparation of polyamic acid solution A1)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), N, N-dimethylacetamide 4416 Dispersion formed by adding colloidal silica having a volume average particle diameter of 80 nm as a lubricant to N, N-dimethylacetamide together with 217 parts by mass of pyromellitic anhydride (PMDA). The body (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) was added so that the amount of silica added was 0.1% by mass relative to the total amount of polymer solids in the polyamic acid solution, and 25 The mixture was stirred for 24 hours at a reaction temperature of 0 ° C. to obtain a brown and viscous polyamic acid solution A1 having a reduced viscosity.

(Preparation of polyamic acid solution A2)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), N, N-dimethylacetamide 4416 Next, 217 parts by mass of pyromellitic anhydride (PMDA) is added and stirred at a reaction temperature of 25 ° C. for 24 hours to give a brown and viscous polyamic acid having a reduced viscosity. Solution A2 was obtained.

(Preparation of polyamic acid solution B1)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4′-diaminodiphenyl ether were added to 8000 parts by mass of N, N-dimethyl. Dispersed in N, N-dimethylacetamide (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) dissolved in acetamide and then dispersed as colloidal silica having a volume average particle size of 80 nm as a lubricant in N, N-dimethylacetamide Was added so that the addition amount of silica was 0.15% by mass with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture was stirred for 24 hours while maintaining the temperature at 20 ° C. or lower to obtain a polyamic acid solution B1. .

(Preparation of polyamic acid solution B2)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4′-diaminodiphenyl ether were added to 8000 parts by mass of N, N-dimethyl. It was dissolved in acetamide and stirred for 24 hours while maintaining the temperature at 20 ° C. or lower to obtain a polyamic acid solution B2.

(Preparation of polyamic acid solution C1)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride and 147 parts by mass of paraphenylenediamine were 4600 parts by mass. Part of N, N-dimethylacetamide dissolved in N, N-dimethylacetamide and then dispersed in N, N-dimethylacetamide as colloidal silica with a volume average particle diameter of 80 nm (Snowtex (registered by Nissan Chemical Industries) Trademark) DMAC-ST30 ”) was added so that the amount of silica added was 0.12% by mass with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture was stirred at a reaction temperature of 25 ° C. for 24 hours. A brown and viscous polyamic acid solution C1 having a water content was obtained.

(Preparation of polyamic acid solution C2)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride and 147 parts by mass of paraphenylenediamine were 4600 parts by mass. Part of N, N-dimethylacetamide was dissolved and stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous polyamic acid solution C2 having a reduced viscosity.

(Preparation of polyamic acid solution D)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 16.2 g (0.05 mol) of 2,2′-bis (trifluoromethyl) benzidine and N-methyl-2-pyrrolidone 109 g and dissolved, then, 11.2 g (0.05 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in portions at room temperature as a solid, and stirred at room temperature for 12 hours. did. Next, 40.0 g of xylene was added as an azeotropic solvent, the temperature was raised to 180 ° C., the reaction was performed for 3 hours, and the azeotropic product water was separated. After confirming that the water had been distilled off, the temperature was raised to 190 ° C. over 1 hour to remove xylene to obtain a reaction solution. In this reaction solution, a dispersion obtained by dispersing colloidal silica having a volume average particle diameter of 80 nm as a lubricant in N, N-dimethylacetamide (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) The addition amount of silica was added so as to be 0.2% by mass with respect to the total amount of polymer solids in the polyamic acid solution to obtain a polyamic acid solution D.

<< Film Production Example 1 >>
The polyamic acid solution A1 is shown as “(b layer) thickness” in Table 1 on the non-slip material surface of a polyethylene terephthalate (PET) film (“A-4100” manufactured by Toyobo Co., Ltd.) as a film forming support. After coating with a comma coater so as to have a dry film thickness and drying at 110 ° C. for 5 minutes, a single-layer polyamic acid film was wound up together with the PET film (without peeling from the PET film).

  A single layer polyamic acid film wound together with a PET film of the film forming support is attached to the unwinding part of the film forming machine, and the polyamic acid solution A2 is shown as “(a layer) thickness” in Table 1 A single layer polyamic acid film surface is coated with a comma coater so as to be thick, dried at 110 ° C. for 20 minutes, and a multilayer polyamic acid film having a two-layer structure is formed on the PET film of the film forming support. Obtained.

  Next, the obtained multilayer polyamic acid film having a two-layer structure is peeled off from the PET film as the film-forming support, and passed through a pin tenter having three heat treatment zones. First stage 150 ° C. × 2 minutes, second stage 220 A third stage 475 ° C. × 4 minutes of heat treatment was performed at a temperature of 2 ° C. for 2 minutes and slit into a width of 500 mm to obtain a multilayered polyimide film. After heat treatment, as a non-polyimide protective film that can be peeled off, a PET film (protective film) provided with a slightly adhesive layer on one side is laminated on the a layer side (in this embodiment, the polyamic acid solution A2 side) and then wound. It was. The properties of the obtained polyimide film are shown in Table 1.

  In addition, the said protective film is stuck for the purpose of preventing the adhesion of foreign matter to the film surface, scratches, and the like, and when being transported by roll-to-roll at a relatively low temperature, it is handled manually. At that time, the operation was performed with the protective film adhered. However, for example, when pressing, laminating, or the like under conditions exceeding 130 ° C., or when performing various treatments on the surface to which the protective film is attached, each operation was performed after the protective film was removed.

<< Film Production Example 2 >>
A polyimide film 2 was obtained in the same manner as in the film production example 1 except that the coating amounts of the polyamic acid solutions A1 and A2 were changed to the dry film thicknesses shown in Table 1, respectively. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 3 >>
The order of application of the polyamic acid solutions A1 and A2 is changed (that is, the b layer is formed of the polyamic acid solution A2 and the a layer is formed of the polyamic acid solution A1), and the application amounts of the polyamic acid solutions A1 and A2 are respectively determined. Except having changed so that it might become a dry film thickness shown in Table 1, it carried out similarly to the film preparation example 1, and obtained the polyimide film 3. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 4 >>
A polyimide film 4 was obtained in the same manner as in the film production example 1 except that the coating amounts of the polyamic acid solutions A1 and A2 were changed to the dry film thicknesses shown in Table 1, respectively. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 5 >>
Except that the polyamic acid solution A2 is not applied (that is, the a layer is not formed), and the coating amount of the polyamic acid solution A1 is changed to the dry film thickness shown in Table 1, film production example 1 and Similarly, a polyimide film 5 was obtained. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 6 >>
Except for changing the polyamic acid solution A1 to B1, changing the polyamic acid solution A2 to B2, and changing the coating amounts of the polyamic acid solutions B1 and B2 to the dry film thicknesses shown in Table 1, respectively. A polyimide film 6 was obtained in the same manner as in Film Production Example 1. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 7 >>
Except for changing the polyamic acid solution A1 to C1, changing the polyamic acid solution A2 to C2, and changing the coating amounts of the polyamic acid solutions C1 and C2 to the dry film thicknesses shown in Table 1, respectively. A polyimide film 7 was obtained in the same manner as in Film Production Example 1. The properties of the obtained polyimide film are shown in Table 1.

<< Film Production Example 8 >>
The polyamic acid solution A1 is changed to D, the polyamic acid solution A2 is not applied (that is, the a layer is not formed), and the applied amount of the polyamic acid solution D is changed to the dry film thickness shown in Table 1. Further, a polyimide film 8 was obtained in the same manner as in Film Production Example 1 except that the temperature in the third heat treatment was 280 ° C. The properties of the obtained polyimide film are shown in Table 1.

<< Films 9, 10 >>
Commercially available “Kapton (registered trademark) 100H” manufactured by Toray DuPont was used as film 9, and commercially available “UPILEX (registered trademark) 25S” manufactured by Ube Industries was used as film 10.

<< Film Processing Examples 1 to 4 >>
With respect to the films 1 to 4, a vacuum plasma treatment was performed on the surface of each polyimide film containing no lubricant (the layer side formed with the polyamic acid solution A2). As vacuum plasma processing, RIE mode using parallel plate type electrodes and RF plasma processing are adopted, Ar gas is introduced into 10 sccm, H ₂ gas is introduced into 5 sccm, and high frequency power of 13.56 MHz is applied. The treatment time was 3 minutes. Table 2 shows the properties of the obtained polyimide films after the treatment. In addition, since the acid treatment (HF process) was not given to each polyimide film after a process obtained here, the crater was not observed.

<< Film Processing Examples 5 to 7 >>
The films 3 to 5 were subjected to vacuum plasma treatment on the layer side (layer side formed with the polyamic acid solution A1) containing the lubricant of each polyimide film, and then the same side as described later. After acid treatment, it was air-dried and placed on a hot plate at 110 ° C. for 1 hour for dehydration treatment. As the vacuum plasma treatment, RIE mode using parallel plate type electrodes and RF plasma treatment are employed, Ar gas is introduced into the vacuum chamber at 10 sccm, H ₂ gas is introduced at 5 sccm, and high frequency power of 13.54 MHz is applied. The treatment time was 3 minutes. The acid treatment was performed by immersing in a 10% by mass HF aqueous solution for 1 minute, washing and drying. Table 2 shows the properties of the obtained polyimide films after the treatment.

<< Film Processing Examples 8 and 9 >>
The films 6 and 7 were subjected to vacuum plasma treatment in the same manner as in the above film treatment example 1. Table 2 shows the properties of the obtained polyimide films after the treatment. In addition, since the acid treatment (HF process) was not given to each polyimide film after a process obtained here, the crater was not observed.

<< Film Processing Examples 10 and 11 >>
The films 8 and 9 were subjected to vacuum plasma treatment in the same manner as in the above film treatment example 1. Table 2 shows the properties of the obtained polyimide films after the treatment. In addition, since the acid treatment (HF process) was not given to each polyimide film after a process obtained here, the crater was not observed.

<< Film Processing Examples 12-15 >>
The films 7 to 10 were subjected to vacuum plasma treatment, acid treatment, air drying and dehydration treatment in the same manner as in the above film treatment example 5. Table 2 shows the properties of the obtained polyimide films after the treatment.

Example 1
While flowing nitrogen gas in a nitrogen-substituted glove box, 3-aminopropyltrimethoxysilane, which is a silane coupling agent (SC agent), is diluted to 0.5% by mass with isopropyl alcohol, and then a support made of an inorganic substance ( Glass (Corning EAGLE XG manufactured by Corning; 100 mm x 100 mm x 0.7 mm thick) that has been cleaned and dried in advance as a substrate is placed on a spin coater, and the silane coupling agent (SC agent) is rotated. It was dropped in the center and rotated at 500 rpm, and then rotated at 2000 rpm so that the entire surface of the support was wetted, and then dried. This was heated for 1 minute on a hot plate heated to 110 ° C. placed in a clean bench to obtain a support having a coupling treatment layer having a thickness of 11 nm.

  Next, the polyimide film obtained in the above-mentioned film processing example 1 was cut into 100 mm × 100 mm (□ 100 mm), and the layer side not containing the lubricant of the polyimide film (in this example, formed with the polyamic acid solution A2). A polyimide film cut into a 70 mm × 70 mm (□ 70 mm) pattern is placed on the surface of the layer side as a mask, and UV irradiation is performed within a range of 70 mm × 70 mm (□ 70 mm), leaving 15 mm each around the periphery of the laminate. Processed.

For UV irradiation, a UV / O ₃ cleaning and reforming apparatus (“SKB1102N-01”) manufactured by Run Technical Service Co., Ltd. and a UV lamp (“SE-1103G05”) are used, and the distance from the UV lamp is about 3 cm. For 2 minutes. At the time of irradiation, no special gas was put in the UV / O ₃ cleaning and reforming apparatus, and the UV irradiation was performed in an air atmosphere at room temperature. The UV lamp emits an emission line with a wavelength of 185 nm (short wavelength capable of generating ozone that promotes inactivation treatment) and a wavelength of 254 nm. At this time, the illuminance is about 20 mW / cm ² (illuminance meter (“ORC UV− M03AUV ") at a wavelength of 254 nm.

Next, it overlaps so that the surface of the coupling treatment layer of the support and the UV irradiation treatment surface (polyamide acid solution A2 side in this embodiment) of the surface-treated polyimide film obtained in the film treatment example 1 face each other. , Using an auto-applied spin coater “MSC800-C-AD type” manufactured by Japan Creates Co., Ltd., after performing pressure treatment with a roller pressure of 0.9 MPa with a pressure increasing valve, then in a hot air oven at 180 ° C. for 50 minutes Heat processing was performed and the laminated body of this invention was obtained.
Table 3 shows the evaluation results of the obtained laminate.

Separately, the surface of the coupling treatment layer in the support provided with the coupling treatment layer obtained above, and the layer side not containing the lubricant of the polyimide film obtained in the film treatment example 1 (this example) Then, the layers are laminated so as to face each other, and the same pressure and heat treatment (lamination using a roll and pressing in an atmospheric pressure) as described above is performed. A sample for measuring the peel strength of the irradiated part was prepared. In each of the following examples, the peel strength of the UV non-irradiated part was measured as in Example 1.
Table 3 shows the evaluation results of the obtained laminate.

(Examples 2 to 4)
Except having changed the polyimide film used in Example 1 into the film obtained in film processing examples 2-4, it carried out similarly to Example 1, and obtained the laminated body of this invention.
Table 3 shows the evaluation results of the obtained laminate.

(Example 5)
A laminate of the present invention was obtained in the same manner as in Example 2, except that a silicon wafer (Si wafer) having a thickness of 0.725 μm was used as the support (substrate) made of an inorganic substance.
Table 3 shows the evaluation results of the obtained laminate.

  In addition, also about each Example other than this Example 2, it carried out similarly except using a silicon wafer instead of glass as a support body which consists of an inorganic substance, and obtained the laminated body, but the evaluation result of the obtained laminated body Each was almost the same as when the glass was used as the support.

(Examples 6 to 16)
Using the treated polyimide film obtained in Treatment Examples 5 to 15 as the polyimide film after film treatment to be superimposed on the support, the coupling agent treated surface of the coupling agent treated glass and each treatment of the treated polyimide film A laminated body of the present invention was obtained in the same manner as in Example 1 except that the layers were superposed so as to face each other.
Table 3 shows the evaluation results of the obtained laminate.

(Examples 17 to 19)
Use a polyimide film that has not been processed as a polyimide film to be superimposed on the support so that the coupling agent-treated surface of the glass treated with the coupling agent and the layer side that does not contain the lubricant of the polyimide film face each other. A laminated body of the present invention was obtained in the same manner as in Example 3, Example 10, or Example 11 except that they were superposed.
Table 3 shows the evaluation results of the obtained laminate.

(Examples 20 to 21)
After performing pressure laminating at 30 ° C. and roll laminating, the inside of the vacuum press machine is evacuated with a rotary pump, pressed in vacuum at 150 ° C. and 8 MPa for 5 minutes, and then in vacuum at 200 ° C. and 8 MPa pressure. A laminate of the present invention was obtained in the same manner as in Example 2 or Example 10 except that the pressing was performed for a minute. The vacuum press used at this time was “11FD” manufactured by Imoto Seisakusho.
Table 3 shows the evaluation results of the obtained laminate.

(Examples 22 to 24)
The present embodiment is the same as Example 2, Example 9 or Example 10 except that the inside of the vacuum press machine is evacuated with a rotary pump and is heated under pressure at 300 ° C. under atmospheric pressure. An inventive laminate was obtained. The vacuum press used at this time was “11FD” manufactured by Imoto Seisakusho.
Table 3 shows the evaluation results of the obtained laminate.

(Example 25)
Using an automatic application type spin coater “MSC800-C-AD type” manufactured by Japan Creates Co., Ltd., on a glass plate (“Corning EAGLE XG” manufactured by Corning: 370 × 470 mm × 0.7 mm thickness), N-2-amino Apply a 0.5 mass% isopropanol solution of ethyl-3-aminopropyltrimethoxysilane, shake the solution at 2000 rpm, stop the rotation, and place the taken out glass plate in a 120 ° C hot plate substituted with dry nitrogen. By placing for 3 minutes, a silane coupling agent treatment was performed to form a silane coupling treatment layer having a thickness of 30 nm.

  Next, the processed film obtained in the film processing example 9 was cut into 350 mm × 450 mm, and a stainless steel metal mask (68 mm × 110 mm rectangular opening was placed through a 5 mm wide shielding portion on the cut processed film. The pattern was arranged in an array and the surface was coated with an insulating coat), and it was confirmed that there was no gap between the metal mask and the glass plate. UV irradiation was performed in the same manner as in 1.

Subsequently, the glass plate and the glass plate on which the silane coupling treatment layer is applied are set to a roll laminator manufactured by MCK, so that the glass-treated surface subjected to UV treatment and the glass plate are subjected to the silane coupling treatment layer. In a heated state, a linear pressure of 50 N / cm (effective estimated pressure of about 1 MPa) was laminated to obtain a film / glass temporary laminate. This film / glass temporary laminate was preheated in a 125 ° C. dry oven for 10 minutes and then heated in an oven at 180 ° C. for 30 minutes to obtain a laminate of the present invention.
Table 3 shows the evaluation results of the obtained laminate.

(Example 26)
A laminate of the present invention was obtained in the same manner as in Example 25 except that the deactivation treatment was changed to the following atmospheric pressure plasma treatment.

The atmospheric pressure plasma treatment uses an atmospheric pressure plasma treatment apparatus having a mechanism of a direct type with a slit-like long head that automatically moves on the workpiece, and a flow rate ratio of nitrogen / oxygen = 95/5 (normally (Pressure-volume ratio) mixed gas was used as the processing gas, and the discharge output was 2 kW. The time during which the glass plate was exposed to plasma was approximately 60 seconds.
Table 3 shows the evaluation results of the obtained laminate.

(Example 27)
A laminate of the present invention was obtained in the same manner as in Example 25 except that the inactivation treatment was changed to the following corona treatment.

The corona treatment was carried out at 40 w / m ^{2 for} 3 minutes in the atmosphere using a conveyor type treatment device manufactured by Kasuga Denki.
Table 3 shows the evaluation results of the obtained laminate.

(Example 28)
In Example 26, the laminated board of this invention was obtained like Example 26 except having changed the used polyimide film into the film obtained in the film processing example 15. FIG.
Table 3 shows the evaluation results of the obtained laminate.

(Example 29) The laminated board of this invention was obtained like Example 27 except having changed the used polyimide film into the film obtained in the film processing example 15 in Example 27.
Table 3 shows the evaluation results of the obtained laminate.

(Comparative Examples 1-3)
The laminated body of the comparative example 1 was obtained like Example 1 except having used the polyimide film obtained without performing a pressurization heat processing.

  Moreover, the polyimide film obtained without performing pressure heat processing was used, and the post-treatment polyimide film obtained in the treatment example 2 or the treatment example 9 was used as the polyimide film after the film treatment to be superimposed on the support. Except for this, the laminates of Comparative Example 2 and Comparative Example 3 were obtained in the same manner as Example 1.

  Table 4 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.

(Comparative Examples 4-5)
Example 1 except that the support was not subjected to a coupling agent treatment, and the treated polyimide film obtained in Treatment Example 2 or 9 was used as a polyimide film after film treatment to be superimposed on the support. In the same manner, laminates of Comparative Example 4 and Comparative Example 5 were obtained. Table 4 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.

(Comparative Examples 6-7)
Except for using the polyimide film obtained without UV irradiation treatment and using the treated polyimide film obtained in Treatment Example 2 or Treatment Example 8 as the polyimide film after film treatment to be superimposed on the support. In the same manner as in Example 1, the laminates of Comparative Example 6 and Comparative Example 7 were obtained.

  Table 4 shows the evaluation results of the obtained laminate. The measurement result was the same value as that of the inactivated non-irradiated part. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement. Moreover, since the inactivation irradiation part is not defined, the result is not described in Table 4.

  For this laminate, a cut was made in the polyimide film, and the film was peeled off from the support. However, the film could not be peeled off successfully, and the film was torn if it was forcibly removed.

(Application examples)
Each of the laminates obtained in each example and each comparative example was covered with a stainless steel frame having an opening and fixed to a substrate holder in the sputtering apparatus. By fixing the substrate holder and the support of the laminate so that they are in close contact with each other and flowing a coolant through the substrate holder, the temperature of the laminate film can be set, and the temperature of the laminate film is set to 2 ° C. Set. First, plasma treatment was performed on the film surface. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 ⁻² Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10 mass%) alloy target is used to form a 1 nm film by DC magnetron sputtering in an argon atmosphere. A nickel-chromium alloy film (underlayer) having a thickness of 11 nm was formed at a rate of / sec. Next, the back surface of the sputtering surface of the substrate is brought into contact with the SUS plate of the substrate holder in which a coolant whose temperature is controlled at 3 ° C. is flown, so that the temperature of the laminated film is set to 2 ° C., and sputtering is performed. went. Then, copper was vapor-deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.22 μm. Thus, the laminated board with a base metal thin film formation film was obtained from each film. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.

Next, a laminated board with a base metal thin film forming film from each film is fixed to a Cu frame, and an electroplating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, gloss, using a copper sulfate plating bath). A thick copper plating layer (thickening layer) having a thickness of 4 μm was formed by immersing in a small amount of the agent and flowing 1.5 Adm ^{2 of} electricity. Subsequently, it was heat-treated at 120 ° C. for 10 minutes and dried to obtain a metallized polyimide film / support laminate.

After applying and drying a photoresist (“FR-200” manufactured by Shipley Co., Ltd.) to each metallized polyimide film / support laminate, the resulting metallized polyimide film / support laminate was subjected to contact exposure with a glass photomask, and further 1.2 mass% KOH. Developed with an aqueous solution. Next, etching was performed with a cupric chloride etching line containing HCl and hydrogen peroxide at 40 ° C. and a spray pressure of ² kgf / cm ² to form a line row of lines / spaces = 20 μm / 20 μm as a test pattern. Next, after electroless tin plating was applied to a thickness of 0.5 μm, annealing treatment was performed at 125 ° C. for 1 hour. Then, the formed pattern was observed with an optical microscope, and the presence or absence of drool, pattern residue, pattern peeling, etc. was evaluated.

  In the laminates of Examples 1 to 15, good patterns with no sagging, pattern residue, and pattern peeling were obtained. Further, after the temperature is increased to 400 ° C. at a rate of temperature increase of 10 ° C./min in a muffle furnace further substituted with nitrogen, swelling and peeling occur even if the temperature is kept at 400 ° C. for 1 hour and then naturally cooled. There was nothing.

  On the other hand, when the laminates of Comparative Examples 1 to 7 were used, film peeling occurred and no good pattern was obtained.

  From the results of the above application examples, the laminate in which the peeling strength between the support and the polyimide film is appropriately adjusted by the production method of the present invention can withstand each process such as metallization, and the subsequent pattern It was confirmed that a good pattern could be formed in the production.

  By carrying out the patterning process on the polyimide film by the manufacturing method of the laminate according to the present invention, and then adopting the manufacturing method in which the support and the polyimide film are superposed, the work steps on the coupling agent surface are reduced. And contamination of the surface of the coupling treatment layer can be suppressed. Therefore, the laminate of the present invention can be used effectively in the production process of a device structure on an ultra-thin polyimide film, on an ultra-thin polymer film excellent in insulation, heat resistance, and dimensional stability. Circuits and devices can be formed with high accuracy. Therefore, in the manufacture of device structures such as sensors, display devices, probes, integrated circuits, and composite devices thereof, amorphous Si thin film solar cells, Se and CIGS compound semiconductor thin film solar cell substrates, and solar cells using them. It is useful and greatly contributes to the industry.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Coupling process layer 3, 3 'UV light blocking mask 4 Polyimide film 5, 5' UV irradiation part 6, 6 'UV non-irradiation part 7, 7', 7 '' A part of polyimide film 8 Gas barrier layer 9 device

Claims (5)

A method for producing a laminate of a support and a polyimide film,
A coupling treatment layer forming step for forming a coupling treatment layer on the surface of the support facing the polyimide film,
A pattern forming step of forming a predetermined pattern by performing a patterning process on a part of the surface of the polyimide film facing the support,
After the coupling treatment layer formation step and the pattern formation step, a pressure heat treatment step is performed in which the support and the polyimide film are overlapped and subjected to pressure heat treatment, and the patterning treatment is an inactivation treatment. The inactivation treatment is performed at least one selected from the group consisting of blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, actinic radiation irradiation treatment, active gas treatment, and chemical treatment. The manufacturing method of the laminated body characterized. Said as the passivation treatment, method for producing a laminate according to claim 1 for performing at least UV irradiation treatment. The manufacturing method of the laminated body of Claim 1 or 2 provided with the plasma processing process which performs a plasma processing with respect to the surface of the side facing the said support body of the said polyimide film before the said pattern formation process. The manufacturing method of the laminated body of Claim 3 provided with the acid treatment process which performs an acid treatment to the said polyimide film between the said plasma treatment process and the said pressurization heat treatment process. A method for producing a structure in which a device is formed on a polyimide film,
Using the laminated body obtained by the manufacturing method of any one of Claims 1-4 which has a support body, a polyimide film, and a coupling process layer,
After forming a device on the polyimide film of this laminated body, the said polyimide film is cut | incised and this polyimide film is peeled from the said support body. The manufacturing method of the device structure characterized by the above-mentioned.